Magnetron Sputtering Vapor Deposition Coating Composition Comprising Light Absorptive Materials

Abstract
A coated article includes a substrate and a metal functional layer over at least a portion of the substrate. The metal functional layer includes a metal alloy, a metal oxide, a metal nitride, a metal oxynitride, or molybdenum. Another coated article includes a glass substrate and a coating over at least a portion of the substrate. The coating includes a dielectric layer, a metal functional layer, and a protective layer. The present invention also provides an insulating glass unit and methods of making a coated article.
Description
BACKGROUND OF THE INVENTION
Field of the Invention

The invention relates generally to a coated article including a substrate and a metal functional layer comprising a metal alloy, metal oxide, metal nitride, metal oxynitride, and/or molybdenum, and methods of making coated articles thereof.


Technical Considerations

Solar control coatings are known in the fields of architectural and vehicle transparencies. These solar control coatings block or filter selected ranges of electromagnetic radiation, such as in the range of solar infrared or solar ultraviolet radiation, to reduce the amount of solar energy entering the vehicle or building. This reduction of solar energy transmittance helps reduce the load on the cooling units of the vehicle or building.


High temperature fabrication processes such as pyrolytic spray process can allow for solar control coatings to be mechanically and chemical durable, such that the coating may be used on the first surface of architectural glass windows. However, the coatings can be rough with poor film quality, and the materials quality and thickness cannot be precisely controlled by this spray technology. As an alternative, magnetron sputtering vapor deposition (MSVD) is an advanced technology for both materials quality and uniformity of thickness and composition. Typical MSVD coatings are soft due to the low temperature process, and do not have good endurance properties. Therefore, it would be desirable to provide a coating that can be deposited by MSVD that has enhanced chemical and mechanical durability.


SUMMARY OF THE INVENTION

A coated article of the invention comprises a substrate and a metal functional layer over at least a portion of the substrate. The metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, and cobalt aluminum iron oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride, or molybdenum.


Another coated article of the invention comprises a glass substrate and a coating over at least a portion of the substrate. The coating comprises a dielectric layer over the substrate, a metal functional layer, and a protective layer over the metal functional layer. The metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, and cobalt aluminum iron oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride, or molybdenum.


The invention also relates to a method of making a coated article. The method comprises providing a substrate and forming a metal functional layer over at least a portion of the substrate. The metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, and cobalt aluminum iron oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride, or molybdenum. The metal functional layer is formed by a process comprising depositing, by a magnetron sputtering vapor deposition method, the metal alloy, metal oxide, metal nitride, metal oxynitride, or molybdenum.


The invention also relates to another method of making a coated article. The method comprises providing a substrate and forming a coating over at least a portion of the substrate. The coating comprises a dielectric layer over the substrate, a metal functional layer, and a protective layer over the metal functional layer. The metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, and cobalt aluminum iron oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride, or molybdenum. The metal functional layer is formed by a process comprising depositing, by a magnetron sputtering vapor deposition method, the metal alloy, metal oxide, metal nitride, metal oxynitride, or molybdenum.


The invention also relates to an insulating glass unit comprising a first ply comprising a No. 1 surface and a No. 2 surface opposing the No. 1 surface and a second ply comprising a No. 3 surface and a No. 4 surface opposing the No. 3 surface. The second ply is spaced from the first ply, and the first ply and the second ply are connected together. A coating is applied over at least a portion of the No. 2 surface or the No. 3 surface, wherein the coating comprises: a dielectric layer over the substrate; a metal functional layer; and a protective layer over the metal functional layer; wherein the metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum.





BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be described with reference to the following drawing figures wherein like reference numbers identify like parts throughout.



FIG. 1A is a side view (not to scale) of an insulating glass unit (IGU) having a coating of the invention.



FIG. 1B is a sectional view (not to scale) of an exemplary transparency having a coating of the invention.



FIG. 2 is a side view (not to scale) of a coating incorporating features of the invention.



FIG. 3 is a side view (not to scale) of another coating incorporating features of the invention.



FIG. 4 is a side view (not to scale) of another coating incorporating features of the invention.



FIG. 5 is a side view (not to scale) of another coating incorporating features of the invention.



FIG. 6 is a side view (not to scale) of another coating incorporating features of the invention.



FIG. 7 is a side view (not to scale) of another coating incorporating features of the invention.



FIG. 8 is a side view (not to scale) of another coating incorporating features of the invention.



FIGS. 9A-9D show Cleveland condensation test results for coated articles of the invention.



FIGS. 10A and 10B show Cleveland condensation test results for coated articles of the invention.



FIGS. 11A-11D show Cleveland condensation test results for coated articles of the invention.





DESCRIPTION OF THE PREFERRED EMBODIMENTS

As used herein, spatial or directional terms, such as “left”, “right”, “inner”, “outer”, “above”, “below”, and the like, relate to the invention as it is shown in the drawing figures.


However, it is to be understood that the invention can assume various alternative orientations and, accordingly, such terms are not to be considered as limiting. Further, as used herein, all numbers expressing dimensions, physical characteristics, processing parameters, quantities of ingredients, reaction conditions, and the like, used in the specification and claims are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical values set forth in the following specification and claims may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical value should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Moreover, all ranges disclosed herein are to be understood to encompass the beginning and ending range values and any and all subranges subsumed therein. For example, a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 1 to 3.3, 4.7 to 7.5, 5.5 to 10, and the like. Further, as used herein, the terms “formed over”, “deposited over”, or “provided over” mean formed, deposited, or provided on but not necessarily in contact with the surface. For example, a coating layer “formed over” a substrate does not preclude the presence of one or more other coating layers or films of the same or different composition located between the formed coating layer and the substrate. As used herein, the terms “polymer” or “polymeric” include oligomers, homopolymers, copolymers, and terpolymers, e.g., polymers formed from two or more types of monomers or polymers. The terms “visible region” or “visible light” refer to electromagnetic radiation having a wavelength in the range of 380 nm to 800 nm. The terms “infrared region” or “infrared radiation” refer to electromagnetic radiation having a wavelength in the range of greater than 800 nm to 100,000 nm. The terms “ultraviolet region” or “ultraviolet radiation” mean electromagnetic energy having a wavelength in the range of 300 nm to less than 380 nm. Additionally, all documents, such as, but not limited to, issued patents and patent applications, referred to herein are to be considered to be “incorporated by reference” in their entirety. As used herein, the term “film” refers to a coating region of a desired or selected coating composition. A “layer” can comprise one or more “films”, and a “coating” or “coating stack” can comprise one or more “layers”. The terms “metal” and “metal oxide” include silicon and silica, respectively, as well as traditionally recognized metals and metal oxides, even though silicon conventionally may not be considered a metal. Thickness values, unless indicated to the contrary, are geometric thickness values.


The discussion of the invention may describe certain features as being “particularly” or “preferably” within certain limitations (e.g., “preferably”, “more preferably”, or “most preferably”, within certain limitations). It is to be understood that the invention is not limited to these particular or preferred limitations but encompasses the entire scope of the disclosure.


Weight percentages (wt. %) of the metal oxides, metal alloys, metal nitrides, or metal oxynitrides, as used herein, are based on the total weight of the metal components and exclude the weight of any oxide, nitride, or oxynitride components. It will be readily appreciated by one having ordinary skill in the art that the weight percentages of the metal functional layer, as used herein, refer to the weight percentages of the metal targets used to deposit the metal functional layer.


The coating of the present invention may be a solar control coating. As used herein, the term “solar control coating” refers to a coating comprised of one or more layers or films that affect the solar properties of the coated article, such as, but not limited to, the amount of solar radiation, for example, visible, infrared, or ultraviolet radiation, reflected from, absorbed by, or passing through the coated article; shading coefficient; emissivity, etc. A solar control coating can block, absorb, or filter selected portions of the solar spectrum, such as, but not limited to, the IR, UV, and/or visible spectrums.


The invention is directed to a coated article. The coated article comprises a substrate. The substrate comprises a metal functional layer over at least a portion of the substrate. The metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, and cobalt aluminum iron oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride, or molybdenum. Optionally, the coated article may also have a protective layer, a base layer, or a dielectric layer. For example, the coated article comprises a substrate that is coated with a coating, where the coating comprises a dielectric layer, a metal functional layer, a protective layer and optionally a second dielectric layer and/or a base layer.


The coated article 10 comprises a substrate 12. The substrate 12 can be of any desired material having any desired characteristics, such as opaque, translucent, or transparent to visible light. For example, the substrate 12 can be transparent or translucent to visible light. By “transparent” is meant having visible light transmission of greater than 0% up to 100%. Alternatively, the substrate 12 can be translucent. By “translucent” is meant allowing electromagnetic energy (e.g., visible light) to pass through but diffusing this energy such that objects on the side opposite the viewer are not clearly visible. Examples of suitable materials include, but are not limited to, plastic substrates (such as acrylic polymers, such as polyacrylates; polyalkylmethacrylates, such as polymethylmethacrylates, polyethylmethacrylates, polypropylmethacrylates, and the like; polyurethanes; polycarbonates; polyalkylterephthalates, such as polyethyleneterephthalate (PET), polypropyleneterephthalates, polybutyleneterephthalates, and the like; polysiloxane-containing polymers; or copolymers of any monomers for preparing these, or any mixtures thereof); ceramic substrates; glass substrates; or mixtures or combinations of any of the above. For example, the substrate 12 can include conventional soda-lime-silicate glass, borosilicate glass, or leaded glass. The glass can be clear glass. By “clear glass” is meant non-tinted or non-colored glass. Alternatively, the glass can be tinted or otherwise colored glass. The glass can be annealed or heat-treated glass. As used herein, the term “heat treated” means tempered or at least partially tempered. The glass can be of any type, such as conventional float glass, and can be of any composition having any optical properties, e.g., any value of visible transmission, ultraviolet transmission, infrared transmission, and/or total solar energy transmission. By “float glass” is meant glass formed by a conventional float process in which molten glass is deposited onto a molten metal bath and controllably cooled to form a float glass ribbon. Examples of float glass processes are disclosed in U.S. Pat. Nos. 4,466,562 and 4,671,155.


The substrate 12 can be, for example, clear float glass or can be tinted or colored glass. The substrate 12 can be of any desired dimensions, e.g., length, width, shape, or thickness. In one exemplary automotive transparency, the substrate 12 can be 1 mm to 10 mm thick, such as 1 mm to 8 mm thick, such as 2 mm to 8 mm, such as 3 mm to 7 mm, such as 5 mm to 7 mm, such as 4 mm to 6 mm thick. In one non-limiting embodiment in which the substrate 12 is an architectural transparency, the substrate 12 may be 1 mm to 30 mm thick, such as 2.5 mm to 25 mm thick, such as 2.5 mm to 10 mm.


Non-limiting examples of glass that can be used for the practice of the invention include clear glass, Starphire®, Solargreen®, Solextra®, GL-20®, GL-35™, Solarbronze®, Solargray® glass, Pacifica@ glass, SolarBlue® glass, and Optiblue® glass, all commercially available from PPG Industries Inc. of Pittsburgh, Pennsylvania.


In some embodiments, the substrate 12 can be a monolithic glazing. By “monolithic” is meant having a single structural support or structural member, e.g. having a single substrate.


The coated article 10 has a metal functional layer 60 deposited over at least a portion of a major surface of a substrate 12. The metal functional layer provides (a) reflectance of electromagnetic radiation in at least a portion of the infrared radiation region of the electromagnetic spectrum, for example, in the solar infrared radiation region and/or the thermal infrared radiation region of the electromagnetic spectrum, and/or (b) absorptivity of electromagnetic radiation in at least a portion of one or more regions of the electromagnetic spectrum, for example, the visible radiation region and/or the infrared radiation region and/or the ultraviolet radiation region of the electromagnetic spectrum.


The metal functional layer 60 can comprise a metal alloy, such as but not limited to a metal alloy comprising silicon and/or cobalt or a metal alloy comprising tungsten. Non-limiting examples of suitable metal alloys include a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy. Alternatively, the metal functional layer 60 can comprise a metal oxide or a metal suboxide, such as but not limited to a metal oxide comprising cobalt. Non-limiting examples of suitable metal oxides for the metal functional layer 60 include cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide.


Alternatively, the metal functional layer 60 can comprise a metal nitride or a metal subnitride, such as but not limited to a metal nitride comprising cobalt. Non-limiting examples of suitable metal nitrides for the metal functional layer 60 include cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride.


Alternatively, the metal functional layer 60 can comprise a metal oxynitride, such as but not limited to a metal oxynitride comprising cobalt. Non-limiting examples of suitable metal oxynitrides for the metal functional layer 60 include cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride.


Alternatively, the metal functional layer 60 can comprise a metal, such as molybdenum.


The metal functional layer 60 may comprise materials with non-magnetic properties. For example, the metal alloy or metal oxide used for the metal functional layer 60 may comprise less than 90 wt. % magnetic materials, such as less than 87 wt. % magnetic materials, based on the total weight of the metal components. The term “magnetic material”, as used herein, refers to materials that produce a magnetic field, and includes the metals iron, cobalt, and nickel, and rare earth metals. The metal alloy, metal oxide, metal nitride, metal oxynitride, or molybdenum used for the metal functional layer 60 may comprise less than 90 wt. % magnetic metals, such as less than 87 wt. % magnetic metals, based on the total weight of the metal components.


In one exemplary embodiment, the metal functional layer 60 comprises cobalt. For example, the metal functional layer 60 may comprise a metal alloy, metal oxide, metal nitride, or metal oxynitride comprising cobalt in the range of from 50 wt. % to 100 wt. %, from 60 wt. % to 100 wt. %, from 60 wt. % to 90 wt. %, from 58 wt. % to 70 wt. %, from 70 wt. % to 89 wt. %, from 75 wt. % to 89 wt. %, or from 80 wt. % to 85 wt. %, based on the total weight of the metal components. In one non-limiting embodiment, the metal functional layer 60 comprises cobalt chromium oxide comprising from 60 wt. % to 100 wt. % cobalt and/or from 0 wt. % to 40 wt. % chromium, from 60 wt. % to 90 wt. % cobalt and 10 wt. % to 40 wt. % chromium, from 58 wt. % to 70 wt. % cobalt and from 30 wt. % to 42 wt. % chromium, from 70 wt. % to 99 wt. % cobalt and from 1 wt. % to 30 wt. % chromium, from 70 wt. % to 88 wt. % cobalt and from 12 wt. % to 30 wt. % chromium, or from 80 wt. % to 85 wt. % cobalt and from 15 wt. % to 20 wt. % chromium.


In some embodiments, the metal functional layer 60 may be substantially free, may be essentially free, or may be completely free of iron. The term “substantially free” as used in this context means the metal functional layer contains less than 1 wt. % iron, “essentially free” means the metal functional layer contains less than 0.1 wt. % iron, and “completely free” means less than 0.01 wt. % iron.


In another exemplary embodiment, the metal functional layer 60 comprises silicon. For example, the metal functional layer 60 may comprise a metal alloy, metal oxide, metal nitride, or metal oxynitride comprising silicon in the range of 50 wt. % to 99 wt. %, from 60 wt. % to 99 wt. %, from 75 wt. % to 99 wt. %, from 80 wt. % to 99 wt. %, from 85 wt. % to 99 wt. %, or from 90 wt. % to 99 wt. %. In one non-limiting embodiment, the metal functional layer 60 comprises a silicon aluminum alloy comprising from 70 wt. % to 100 wt. % silicon and from 0 wt. % to 30 wt. % aluminum, such as from 80 wt. % to 95 wt. % silicon and from 5 wt. % to 20 wt. % aluminum; such as from 85 wt. % to 99 wt. % silicon and from 1 wt. % to 15 wt. % aluminum, such as from 85 wt. % to 95 wt. % silicon and from 5 wt. % to 15 wt. % aluminum, or from 90 wt. % to 95 wt. % silicon and from 5 wt. % to 10 wt. % aluminum.


In another exemplary embodiment, the metal functional layer comprises silicon and cobalt. For example, the metal functional layer 60 may comprise a metal alloy, metal oxide, metal nitride, or metal oxynitride comprising silicon in the range of 30 wt. % to 85 wt. % and cobalt in the range of 15 wt. % to 70 wt. %, such as from 50 wt. % to 90 wt. % silicon and from 10 wt. % to 50 wt. % cobalt, such as from 50 wt. % to 70 wt. % silicon and from 30 wt. % to 50 wt. % cobalt, such as from 65 wt. % to 75 wt. % silicon and from 25 wt. % to 35 wt. % cobalt.


The metal functional layer 60 can have any desired thickness, such as in the range of from 1 nm to 100 nm, from 5 nm to 50 nm, from 10 nm to 50 nm, from 10 nm to 45 nm, from 20 nm to 40 nm, from 20 nm to 50 nm, from 20 nm to 60 nm, from 30 nm to 45 nm, from 10 nm to 35 nm, or from 20 nm to 30 nm.


The coated article 10 can include a protective layer 80, which, for example in the non-limiting embodiment shown in FIG. 2, is deposited over the metal functional layer 60, to assist in protecting the underlying layers, such as the metal functional layer, from mechanical and chemical attack during processing. The protective layer 80 can be the outermost layer of the coating 30. The protective layer 80 can be an oxygen barrier coating layer to prevent or reduce the passage of ambient oxygen into the underlying layers of the coating 30, such as during heating or bending. The protective layer 80 can be of any desired material or mixture of materials. For example, the protective layer can comprise a metal oxide layer, a metal nitride layer, or mixtures thereof. In one exemplary embodiment, the protective layer 80 can include a layer having one or more metal oxide materials, such as but not limited to oxides of aluminum, silicon, or mixtures thereof. For example, the protective coating 80 can be a single coating layer comprising in the range of 0 wt. % to 100 wt. % alumina and/or 100 wt. % to 0 wt. % silica, such as 5 wt. % to 95 wt. % alumina 45 and 95 wt. % to 5 wt. % silica, such as 10 wt. % to 90 wt. % alumina and 90 wt. % to 10 wt. % silica, such as 15 wt. % to 90 wt. % alumina and 85 wt. % to 10 wt. % silica, such as 50 wt. % to 75 wt. % alumina and 50 wt. % to 25 wt. % silica, such as 50 wt. % to 70 wt. % alumina and 50 wt. % to 30 wt. % silica, such as 35 wt. % to 100 wt. % alumina and 65 wt. % to 0 wt. % silica, e.g., 70 wt. % to 90 wt. % alumina and 30 wt. % to 10 wt. % silica, e.g., 75 wt. % to 85 wt. % alumina and 25 wt. % to 15 wt. % of silica, e.g., 88 wt. % alumina and 12 wt. % silica, e.g., 65 wt. % to 75 wt. % alumina and 35 wt. % to 25 wt. % silica, e.g., 70 wt. % alumina and 30 wt. % silica, e.g., 60 wt. % to less than 75 wt. % alumina and greater than 25 wt. % to 40 wt. % silica. Other materials, such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorous, titanium, zirconium, and/or oxides thereof, can also be present, such as to adjust the refractive index of the protective layer 80, 92. In one non-limiting embodiment, the refractive index of the protective layer 80, 92 can be in the range of 1 to 3, such as 1 to 2, such as 1.4 to 2, such as 1.4 to 1.8.


In one non-limiting embodiment, the protective layer 80 is a combination silica and alumina coating. The protective layer 80 can be sputtered from two cathodes (e.g., one silicon and one aluminum) or from a single cathode containing both silicon and aluminum. This silicon/aluminum oxide protective layer 80 can be written as SixAlIxO(1.5+x)/2, where x can vary from greater than 0 to less than 1.


In another non-limiting embodiment, the protective layer 80 comprises a combination of titania and alumina.


In one non-limiting embodiment, the protective layer 80 may be comprised of silicon oxide (SiOx), silicon nitride (Si3N4 or SiNx), silicon oxynitride (SiOxNy), silicon aluminum oxide (SiAlOx) silicon aluminum nitride (SiAlNx), silicon aluminum oxynitride (SiAlOxNy), a mixture thereof, and/or an alloy thereof, and which may provide increased durability to the metal functional layer 60. The protective layer 80 may be formed of silicon nitride deposited with other materials having superior electrical conductivity to improve sputtering of the silicon. For example, during deposition, the silicon cathode can include a small amount (e.g., up to 20 wt. %, up to 15 wt. %, up to 10 wt. %, or up to 5 wt. %) of aluminum to improve sputtering. In which case, the resultant silicon nitride protective layer would include a small percentage of aluminum, e.g., up to 15 wt. % aluminum, e.g., up to 10 wt. % aluminum, e.g., up to 5 wt. % aluminum. A coating layer deposited from a silicon cathode having up to 10 wt. % aluminum (added to enhance the conductivity of the cathode) is referred to herein as “a silicon nitride” layer, even though a small amount of aluminum may be present. The small amount of aluminum in the cathode (e.g., less than or equal to 15 wt. %, such as less than or equal to 10 wt. %, such as less than or equal to 5 wt. %) is believed to form aluminum nitride in the predominantly silicon nitride protective layer 80. The protective layer 80 may be formed in a nitrogen atmosphere; however, it is to be understood that other gasses, such as oxygen, may be present in the atmosphere during the deposition of the protective layer 80.


The protective layer can be of any desired thickness. The protective layer 80 can have a thickness in the range of from 1 nm to 250 nm, from 1 nm to 150 nm, from 5 nm to 150 nm, from 10 nm to 120 nm, from 100 nm to 140 nm, from 5 nm to 70 nm, from 30 nm to 70 nm, from 5 nm to 30 nm, or from 10 nm to 30 nm. The protective layer 80 is the outermost layer of the coated article. Further, the protective layer 80 can be of non-uniform thickness. By “non-uniform thickness” is meant that the thickness of the protective layer 80 can vary over a given unit area, e.g., the protective layer 80 can have high and low spots or areas.


In another non-limiting embodiment, the protective coating 80 can be a multilayer coating comprising a first film and a second film formed over the first film. The first film can comprise alumina, silica, titania, zirconia, tin oxide, or mixtures thereof. In one specific non-limiting embodiment, the first film can comprise alumina or a mixture or alloy comprising alumina and silica. For example, the first film can comprise a silica/alumina mixture having greater than 5 wt. % alumina, such as greater than 10 wt. % alumina, such 30 as greater than 15 wt. % alumina, such as greater than 30 wt. % alumina, such as greater than 40 wt. % alumina, such as 50 wt. % to 70 wt. % alumina, such as in the range of 60 wt. % to 100 wt. % alumina and 0 wt. % to 40 wt. % silica, e.g. 60 wt. % alumina and 40 wt. % silica. In another example, the first layer can comprise zinc stannate. In another example, the first film can comprise zirconia. In one non-limiting embodiment, the first film can have a thickness in the range of greater than 0 nm to 1,000 nm, such as 10 nm to 25 nm, such as 10.1 nm to 25 nm, such as 15 nm to 20 nm, such as 16 nm.


The second film of the protective layer 80 may comprise, for example, a metal oxide or metal nitride. The second film can be titania, alumina, silica, zirconia, tin oxide, a mixture thereof, or an alloy thereof. For example, the second film may include a mixture of titania and alumina; a mixture of titania and silica; or zirconia. An example of the second film can comprise a titania/alumina mixture having 40 wt. % to 60 wt. % alumina, and 40 wt. % to 60 wt. % titania; 45 wt. % to 55 wt. % alumina, and 45 wt. % to 55 wt. % titania; 48 wt. % to 52 wt. % alumina, and 48 wt. % to 52 wt. % titania; 49 wt. % to 51 wt. % alumina, and 49 wt. % to 51 wt. % titania; or 50 wt. % alumina, and 50 wt. % titania. An example of the second film may include titanium aluminum oxide (TiAlO). Another example of the second film is a silica/alumina mixture having greater than 40 wt. % silica, such as greater than 50 wt. % silica, such as greater than 60 wt. % silica, such as greater than 70 wt. % silica, such as greater than 80 wt. % silica, such as in the range of 80 wt. % to 90 wt. % 45 silica and 10 wt. % to 20 wt. % alumina, e.g., 85 wt. % silica and 15 wt. % alumina. In one non-limiting embodiment, the second film can have a thickness in the range of greater than 0 nm to 2,000 nm, such as 5 nm to 500 nm, such as 5 nm to 200 nm, such as 10 nm to 100 nm, such as 20 nm to 50 nm, such as 22 nm to 35 nm, such as 22 nm. Non-limiting examples of suitable protective layers are described, for example, in U.S. Patent Application Publication Nos. 2004/0106017 A1; 2002/0172775 A1; 2003/0228484 A1; 2004/0023080 A1; 2004/0023038 A1; and 2003/0228476 A1.


In non-limiting examples, the protective layer 80 may include an additional third film formed over the second film. This third film can be any of the materials used to form the first film or the second film. The third film, for example, can comprise alumina, silica, titania, zirconia, tin oxide, or mixtures thereof. For example, the third film can comprise a mixture of silica and alumina. In another example, the third film comprises zirconia.


In one non-limiting embodiment, the coated article 10 can optionally include a base layer 50, which, for example as shown in FIG. 3, may be deposited over the substrate 12 and under the metal functional layer 60. The base layer 50 may provide the coating 30 with various performance advantages, such as acting as a sodium ion barrier between the substrate 12 and the overlying coating layers. The base layer 50 can comprise any of the materials described above with respect to the outermost protective layer 80. For example the base layer may be comprised of tin oxide (SnOx), silicon oxide (SiOx), silicon nitride (Si3N4 or SiNx), silicon oxynitride (SiOxNx), silicon aluminum oxide (SiAlOx), silicon aluminum nitride (SiAlNx), silicon aluminum oxynitride (SiAlOxNx), a mixture thereof, and/or an alloy thereof.


The base layer 50 can be a multilayer coating comprising a first film and a second film formed over the first film. In one non-limiting embodiment, the base layer optionally comprises one or more films, wherein each film comprises SnOx, SiOx, Si3N4, SiOxNx, SiAlOx, SiAlNx, or SiAlOxNx. For example, the base layer may optionally comprise two films, wherein each film comprises SiAlOx or SiAlNx.


In one non-limiting embodiment, the base layer 50 may optionally be comprised of a film of a metal nitride, such as Si3N4 and/or SiAlN, disposed over and in contact with a film of metal oxynitride, such as SiAlON. Examples of metal oxynitride films also, or alternatively, may include alloys and/or mixtures of a metal nitride.


The optional base layer 50 can be of any desired thickness. The optional base layer 50 can have a thickness in the range of from 1 nm to 250 nm, from 1 nm to 150 nm, from 5 nm to 150 nm, from 10 nm to 120 nm, from 15 nm to 100 nm, from 30 nm to 110 nm, from 100 nm to 140 nm, from 70 nm to 110 nm, or from 30 nm to 80 nm.


In one non-limiting embodiment, the coated article 10 can include at least one dielectric layer, such as dielectric layer 40, which for example as shown in FIGS. 4, 5, and 6, is deposited over the substrate 12 and under the metal functional layer 60. As shown in FIGS. 4 and 5, the dielectric layer 40 is deposited over the substrate 12 and is under the metal functional layer 60. In another embodiment, the coated article 10 may include a dielectric layer 40 that is deposited over the substrate 12 and is under the base layer 50 (FIG. 6).


Alternatively, the coated article 10 can include a dielectric layer 70, which is deposited over the metal functional layer 60 and under the protective layer 80 (FIG. 7). In another non-limiting embodiment, the dielectric layer 70 is over the protective layer 80 and is the outermost layer (FIG. 8).


The dielectric layer(s) 40, 70 can be a single layer or can comprise more than one film of antireflective materials and/or dielectric materials, such as, but not limited to, metal oxides, oxides of metal alloys, metal nitrides, metal oxynitrides, or mixtures thereof. The dielectric layer(s) 40, 70 can be transparent to visible light. Examples of suitable metal oxides for the dielectric layer(s) 40, 70 include oxides of titanium, hafnium, zirconium, niobium, zinc, bismuth, lead, indium, tin, and mixtures thereof. These metal oxides can have small amounts of other materials, such as manganese in bismuth oxide, tin in indium oxide, etc. Additionally, oxides of metal alloys or metal mixtures can be used, such as oxides containing zinc and tin (e.g., zinc stannate, defined below), oxides of indium-tin alloys, silicon nitrides, silicon aluminum nitrides, or aluminum nitrides. Further, doped metal oxides, such as antimony or indium doped tin oxides or nickel or boron doped silicon oxides, can be used.


The dielectric layer(s) 40, 70 can be a substantially single phase film, such as a metal oxide film, e.g., zinc stannate, or can be a mixture of phases composed of zinc and tin oxides or can be composed of a plurality of films. For example, the dielectric layer(s) may comprise one or more films selected from zinc tin oxides, zinc oxide, silica, silicon aluminum oxides, silicon nitride, aluminum nitride, silicon aluminum nitrides, titanium oxides, and titanium nitrides.


The dielectric layer(s) 40, 70 (whether a single film or multiple film layer) can have any thickness, such as in the range of from 1 nm to 200 nm, from 1 nm to 150 nm, from 1 nm to 100 nm, from 5 nm to 140 nm, from 5 nm to 100 nm, from 10 nm to 50 nm, from 30 nm to 70 nm, from 80 nm to 120 nm, from 100 nm to 140 nm, or from 1 nm to 10 nm.


The coated article 10 may comprise more than one dielectric layer. Each dielectric layer may comprise the same or different materials and have the same or different thickness as the other dielectric layers in the coated article. For example, the coated article 10 may comprise at least two dielectric layers. In one non-limiting embodiment, the coated article may have a first dielectric layer 40 that is directly over the substrate 12 and under the metal functional layer 60 and a second dielectric layer 70 that is directly over the metal functional layer 60 and under the protective layer 80, as shown in FIG. 5.


In one non-limiting embodiment, the coated article 10 can optionally include a primer layer over the metal functional layer 60. The primer layer can be a single film or a multiple film layer. The primer layer can include an oxygen-capturing material that can be sacrificial during the deposition process to prevent degradation or oxidation of the metal functional layer 60 during the sputtering process or subsequent heating processes. The primer layer can also absorb at least a portion of electromagnetic radiation, such as, visible light, passing through the coating 30. Examples of materials useful for the primer layer include titanium, silicon, silicon dioxide, silicon nitride, silicon oxynitride, nickel, zirconium, aluminum, cobalt, chromium, titanium, aluminum, an alloy thereof, or a mixture thereof. In one non-limiting embodiment, the primer layer comprises titanium, titanium and aluminum, or zinc and aluminum, which are deposited as a metal and at least a portion of the titanium, or titanium and aluminum, or zinc and aluminum are subsequently oxidized. In another embodiment, the primer layer comprises a nickel chromium alloy, such as, Inconel. In another embodiment, the primer layer comprises a cobalt-chromium alloy, such as, Stellite®.


The primer layer can have a thickness in the range of from 0.5 nm to 5 nm, such as, from 1 nm to 4 nm, such as, from 1 nm to 2.5 nm.


The invention is also related to a coated article comprising a glass substrate and a coating over at least a portion of the substrate. The coating comprises a dielectric layer over the substrate, a metal functional layer, and a protective layer over the metal functional layer. The metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, or a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum. The dielectric layer, the metal functional layer, and the protective layer of the coating can be any of the layers previously described herein. Optionally, the coating further comprises a second dielectric layer, primer layer, and/or a base layer. The optional second dielectric layer, optional primer layer, and optional base layer of the coating are any of the layers previously described herein.


An exemplary non-limiting coated article 10 of the invention is shown in FIG. 2. The coated article 10 includes a metal functional layer 60 that is deposited over and optionally in direct contact with the substrate 12. The coated article 10 further includes a protective layer 80 that is deposited over and optionally in direct contact with the metal functional layer 60. The metal functional layer 60 and the protective layer 80 form the coating 30 that is over and optionally in direct contact with at least a portion of substrate 12. The substrate 12 may be glass.


Another exemplary non-limiting coated article 10 of the invention is shown in FIG. 3. The coated article 10 includes a base layer 50 that is deposited over and optionally in direct contact with the substrate 12. The coated article 10 further includes a metal functional layer 60 that is deposited over and optionally in direct contact with the base layer 50. The coated article 10 further includes an outermost protective layer 80 that is deposited over and optionally in direct contact with the metal functional layer 60. The base layer 50, the metal functional layer 60, and the protective layer 80 form the coating 30 that is over and optionally in direct contact with at least a portion of substrate 12. The substrate 12 may be glass.


Another exemplary non-limiting coated article 10 of the invention is shown in FIG. 4. The coated article 10 includes a dielectric layer 40 that is deposited over and optionally in direct contact with at least a portion of the substrate 12. The coated article further includes a metal functional layer 60 that is deposited over and optionally in direct contact with the dielectric layer 40. The coated article 10 further includes a protective layer 80 that is deposited over and optionally in direct contact with the metal functional layer 60. The dielectric layer 40, the metal functional layer 60, and the protective layer 80 form the coating 30 that is over and optionally in direct contact with at least a portion of substrate 12. The substrate 12 may be glass.


Another exemplary non-limiting coated article 10 of the invention is shown in FIG. 5. The coated article 10 includes a first dielectric layer 40 that is deposited over and optionally in direct contact with at least a portion of the substrate 12. The coated article 10 further includes a metal functional layer 60 that is deposited over and optionally in direct contact with the dielectric layer 40. The coated article 10 further includes a second dielectric layer 70 that is deposited over and optionally in direct contact with the metal functional layer 60. The coated article 10 further includes a protective layer 80 that is deposited over and optionally in direct contact with the second dielectric layer 70. The first dielectric layer 40, the metal functional layer 60, the second dielectric layer 70, and the protective layer 80 form the coating 30 that is over and optionally in direct contact with at least a portion of substrate 12. The substrate 12 may be glass.


Another exemplary non-limiting coated article 10 of the invention is shown in FIG. 6. The coated article 10 includes a first dielectric layer 40 that is deposited over and optionally in direct contact with at least a portion of the substrate 12. The coated article 10 further includes a base layer 50 that is deposited over and optionally in direct contact with the dielectric layer 40. The coated article 10 further includes a metal functional layer 60 that is deposited over and optionally in direct contact with the base layer 50. The coated article 10 further includes a protective layer 80 that is deposited over and optionally in direct contact with the metal functional layer 60. The dielectric layer 40, the base layer 50, the metal functional layer 60, and the protective layer 80 form the coating 30 that is deposited over and optionally in direct contact with at least a portion of substrate 12. The substrate 12 may be glass.


Another exemplary non-limiting coated article 10 of the invention is shown in FIG. 7. The coated article 10 includes a metal functional layer 60 that is deposited over and optionally in direct contact with the substrate 12. The coated article 10 further includes a dielectric layer 70 that is deposited over and optionally in direct contact with the metal functional layer 60. The coated article 10 further includes a protective layer 80 that is deposited over and optionally in direct contact with the dielectric layer 70. The metal functional layer, the dielectric layer, and the protective layer form the coating 30 that is deposited over and optionally in direct contact with at least a portion of substrate 12. The substrate 12 may be glass.


Another exemplary non-limiting coated article 10 of the invention is shown in FIG. 8. The coated article 10 includes a metal functional layer 60 that is deposited over and optionally in direct contact with the substrate 12. The coated article 10 further includes a protective layer 80 that is deposited over and optionally in direct contact with the metal functional layer 60. The coated article 10 further includes a dielectric layer 70 that is deposited over and optionally in direct contact with protective layer 80. The metal functional layer 60, the protective layer 80, and the dielectric layer 70 form the coating 30 that is deposited over and optionally in direct contact with at least a portion of substrate 12. The substrate 12 may be glass.


The dielectric layer(s) 40, 70, the optional base layer 50, the metal functional layer 60, the protective layer 80, and the optional primer layer can be deposited by any conventional method, such as but not limited to conventional chemical vapor deposition (CVD) and/or physical vapor deposition (PVD) methods. Examples of CVD processes include spray pyrolysis. Examples of PVD processes include electron beam evaporation and vacuum sputtering (such as magnetron sputter vapor deposition (MSVD)). Other coating methods could also be used, such as but not limited to sol-gel deposition. In one non-limiting embodiment, the layers of the coating 30 can be deposited by MSVD. Examples of MSVD coating devices and methods will be well understood by one of ordinary skill in the art and are described, for example, in U.S. Pat. Nos. 4,379,040; 4,861,669; 4,898,789; 4,898,790; 4,900,633; 4,920,006; 4,938,857; 5,328,768; and 5,492,750. In one non-limiting embodiment, a cobalt chromium alloy is used as a magnetron sputtering target to deposit metal functional layer 60.


The coating 30 of the present invention can provide the coated article 10 with desirable physical properties including, but not limited to durability properties, such as humidity resistance and chemical resistance. With some non-limiting embodiments, the presence of the dielectric layer(s) 40, 70 and/or the protective layer 80 were found to enhance the durability of the coating.


In one non-limiting practice of the invention, the coated article 10 passes the conventional Cleveland Condensation test (CCC test) as measured in a Cleveland Condensation Chamber (a Q.C.T. Condensation Tester commercially available from the Q-Panel Company of Cleveland, Ohio) with a deionized (DI) water chamber at about 60 degrees Celsius (° C.). With some embodiments, the coated articles 10 having the dielectric layer(s) 40, 70 pass the CCC test compared to coated articles without the dielectric layer(s) 40, 70. In one non-limiting embodiment, the coated article 10 has a transmittance elliptical color difference (DECMC, T) of less than 10 after 50 days, such as less than 7, less than 5, less than 1, or less than 0.5. In one non-limiting embodiment the coated article 10 has a film side reflectance elliptical color difference (DECMC, Rf) of less than 20 after 50 days, such as less than 15, or less than 10, less than 5, less than 1, or less than 0.5. In one non-limiting embodiment, the coated article 10 has a glass side reflectance elliptical color difference (DECMC, Rg) of less than 18 after 50 days, such as less than 15, or less than 13.


In one non-limiting practice of the invention, the coated article 10 may have a film loss of less than 12%, such as less than 10%, after 30 minutes immersion in 10N (27.5%) sulfuric acid at 52° C. (Standard Chemical Durability Test). With some embodiments, coated articles 10 comprising the dielectric layer(s) 40, 70 pass the Standard Chemical Durability test compared to coated articles without the dielectric layer(s) 40, 70.


The materials used for the coating layers, such as the metal functional layer 60, may be selected to achieve desired color properties for the coated article 10. The coating 30 may consist essentially of the materials as described herein such that the desired color properties of the coating are achieved. For example, a coating 30 consisting essentially of the materials as described herein may include additional materials provided that the color properties of the coating are not affected. The color coordinates a*, b*, and L* are those of the conventional CIE (1931) and CIELAB systems that will be understood by one of ordinary skill in the art.


In one non-limiting practice of the invention, the coated article 10 has a transmittance L* in the range of 55 to 75. For example, in the range of 60 to 75, 59 to 70, 67 to 73, or 70 to 75.


In one non-limiting practice of the invention, the coated article 10 has a transmittance (T) a* in the range of 0.0 to 3.5. For example, in the range of 0.0 to 3.0, 0.5 to 3.0, or 0.8 to 3.0.


In one non-limiting practice of the invention, the coated article 10 has a transmittance (T) b* in the range of 6.5 to 11.5. For example, in the range of 6.5 to 11.0, 7.0 to 11.0, or 7.5 to 11.0.


In one non-limiting practice of the invention, the coated article 10 has a visible light transmittance (LTA) in the range of 20 to 50. For example, in the range of 25 to 50, 30 to 40, 38 to 48, or 42 to 47.


In one non-limiting practice of the invention, the coated article 10 has a film side reflection (Rf) L* in the range of 35 to 70. For example, in the range of 35 to 65, 40 to 65, 40 to 55, or 60 to 65.


In one non-limiting practice of the invention, the coated article 10 has an Rf a* in the range of −5.0 to −1.0. For example, in the range of −5.0 to −2.0, or −5.0 to −3.0.


In one non-limiting practice of the invention, the coated article 10 has an Rf b* in the range of −3.5 to 7.5. For example, in the range of −3.0 to 7.5, −3.0 to 5.0, 0.0 to 7.5, or 1.0 to 7.0.


In one non-limiting practice of the invention, the coated article 10 has a glass side reflection (Rg) L* in the range of 40 to 65. For example, in the range of 40 to 60, 45 to 60, 50 to 65, 50 to 60, 55 to 65, or 55 to 60.


In one non-limiting practice of the invention, the coated article 10 has an Rg a* in the range of −7.5 to −4.0. For example, in the range of −7.0 to −4.0, −6.0 to −4.0, −7.5 to −5.0, −7.0 to −5.0, −7.5 to −6.0, or −7.0 to −6.0.


In one non-limiting practice of the invention, the coated article 10 has an Rg b* in the range of −11.0 to 4.0. For example, in the range of −11.0 to 3.5, 1.0 to 4.0, 1.0 to 3.5, −11.0 to −7.0, −9.5 to −7.5, or −6.5 to −5.0.


Certain embodiments of the present invention are particularly useful for solar control coatings for architectural transparencies and automotive transparencies.


The present invention is also related to a method of making a coated article. A substrate is provided. A metal functional layer is formed over at least a portion of the substrate, wherein the metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, and cobalt aluminum iron oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride, or molybdenum. The metal functional layer is formed by a process comprising depositing, by a magnetron sputtering vapor deposition method, the metal alloy, metal oxide, metal nitride, metal oxynitride, or molybdenum. The method may also optionally further comprises forming a protective layer. The protective layer can be any of the protective layers described herein. The method may also optionally further comprise forming at least one dielectric layer. The at least one dielectric layer can be any one of the dielectric layers described herein. The method may also optionally further comprise forming a base layer. The optional base layer may be any of the optional base layers described herein. The method may also optionally further comprise forming a primer layer. The optional primer layer may be any of the primer layers described herein.


The present invention is also related to a method of making a coated article, wherein a substrate is provided and a coating is formed over at least a portion of the substrate. The coating comprises a dielectric layer over the substrate, a metal functional layer, and a protective layer over the metal functional layer. The metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum. The metal functional layer is formed by a process comprising depositing, by a magnetron sputtering vapor deposition method, the metal alloy, metal oxide, metal nitride, metal oxynitride, or molybdenum. The metal functional layer can be any of the metal functional layers described herein. The dielectric layer and the protective layer can be any of the dielectric layers and protective layers described herein. The coating may optionally further comprise a second dielectric layer. The second dielectric layer may be any of the dielectric layers described herein. The coating may optionally further comprise a base layer. The optional base layer may be any of the base layers described herein. The coating may optionally further comprise a primer layer. The optional primer layer may be any of the primer layers described herein.


The coated articles described herein can be used in an architectural transparency, such as, but not limited to, an insulating glass unit. As used herein, the term “architectural transparency” refers to any transparency located on a building, such as, but not limited to, windows and sky lights. However, it is to be understood that the invention is not limited to use with such architectural transparencies but could be practiced with transparencies in any desired field, such as, but not limited to, laminated or non-laminated residential and/or commercial windows, insulating glass units, and/or transparencies for land, air, space, above water and underwater vehicles. Therefore, it is to be understood that the specifically disclosed exemplary embodiments are presented simply to explain the general concepts of the invention, and that the invention is not limited to these specific exemplary embodiments. Additionally, while a typical “transparency” can have sufficient visible light transmission such that materials can be viewed through the transparency, in the practice of the invention, the “transparency” need not be transparent to visible light but may be translucent or opaque.


A non-limiting insulating glass unit 110 incorporating features of the invention is provided in FIG. 1A. The insulating glass unit 110 includes a first ply 112 with a first major surface 114 (No. 1 surface) and an opposed second major surface 116 (No. 2 surface). In the illustrated non-limiting embodiment, the first major surface 114 faces the building exterior, i.e., is an outer major surface, and the second major surface 116 faces the interior of the building. The insulating glass unit 110 also includes a second ply 118 having an outer (first) major surface 120 (No. 3 surface) and an inner (second) major surface 122 (No. 4 surface) and spaced from the first ply 112. In some embodiments, the insulating glass unit 110 includes a third ply with a No. 5 surface and an opposed No. 6 surface. This numbering of the ply surfaces is in keeping with conventional practice in the fenestration art.


The plies 112, 118 can have any desired visible light, infrared radiation, or ultraviolet radiation transmission and/or reflection. For example, the plies 112, 118 can have a visible light transmission of any desired amount, e.g., greater than 0% up to 100%. The plies 112, 118 can each be, for example, clear float glass or can be tinted or colored glass or one ply 112, 118 can be clear glass and the other ply 112, 118 colored glass. Although not limiting to the invention, examples of glass suitable for the first ply 112 and/or second ply 118 are described in U.S. Pat. Nos. 4,746,347; 4,792,536; 5,030,593; 5,030,594; 5,240,886; 5,385,872; and 5,393,593.


The first and second plies 112, 118 can be connected together in any suitable manner, such as by being adhesively bonded to a conventional spacer frame 124. A gap or chamber 126 is formed between the two plies 112, 118. The chamber 126 can be filled with a selected atmosphere, such as air, or a non-reactive gas such as argon or krypton gas. A coating 130 is formed over at least a portion of one of the plies 112, 118, such as, but not limited to, over at least a portion of the No. 2 surface 116 or at least a portion of the No. 3 surface 120. Although, the coating 130 could also be on the No. 1 surface 114 or the No. 4 surface 122, if desired. The coating 130 may comprise, consist essentially of, or consist of any of the coatings described herein. Examples of insulating glass units are found, for example, in U.S. Pat. Nos. 4,193,236; 4,464,874; 5,088,258; and 5,106,663.


The coated articles described herein can be used in a vehicle transparency, such as, a window or sunroof. A non-limiting vehicle transparency 210 incorporating features of the invention is provided in FIG. 1B. For clarity, seals, connectors, and opening mechanisms are not shown, nor is the complete vehicle. The transparency includes a first ply 212 with a first major surface 214 (No. 1 surface) and an opposed second major surface 216 (No. 2 surface) mounted in the body of a vehicle 218 (shown in part). In the illustrated non-limiting embodiment, the first major surface 214 faces the vehicle's exterior, and thus is an outer major surface, and the second major surface 216 faces the interior of the vehicle. Non-limiting examples of a vehicle body include: an automobile roof in the case of a sunroof, an automobile door or frame in the case of an automobile window, or a fuselage of an airplane.


The transparency may be affixed to a mechanism by which the transparency, such as, a car window or sunroof, can be opened and closes, as is broadly known in the vehicular arts. A coating 230 is shown as formed over the No. 1 surface 214, but it may be formed over at least a portion of the No. 2 surface 216. The coating 230 may comprise, consist essentially of, or consist of any of the coatings described herein.


The invention is further described in the following numbered clauses:


Clause 1. A coated article comprising: a substrate; and a metal functional layer over at least a portion of the substrate; wherein the metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, and cobalt aluminum iron oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride, or molybdenum.


Clause 2. The coated article of clause 1, wherein the metal functional layer comprises less than 90 wt. % magnetic metals.


Clause 3. The coated article of clause 1 or 2, wherein the metal functional layer has a thickness in the range of 20 nm to 40 nm, from 20 nm to 60 nm, from 30 nm to 45 nm, or from 20 nm to 30 nm.


Clause 4. The coated article of any one of clauses 1 to 3, wherein the metal functional layer comprises from 60 wt. % to 100 wt. % cobalt, from 60 wt. % to 90 wt. % cobalt, or from 58 wt. % to 70 wt. % cobalt.


Clause 5. The coated article of any one of clauses 1 to 4, wherein the metal functional layer comprises cobalt chromium oxide.


Clause 6. The coated article of any one of clauses 1 to 5, wherein the metal functional layer comprises from 60 wt. % to 100 wt. % cobalt and from 0 wt. % to 40 wt. % chromium, from 60 wt. % to 90 wt. % cobalt and from 10 wt. % to 40 wt. % chromium, or from 70 wt. % to 88 wt. % cobalt and from 12 wt. % to 30 wt. % chromium.


Clause 7. The coated article of any one of clauses 1 to 3, wherein the metal functional layer comprises from 60 wt. % to 99 wt. % silicon.


Clause 8. The coated article of any one of clauses 1 to 3 or 7, wherein the metal functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.


Clause 9. The coated article of any one of clauses 1 to 3, 7, or 8, wherein the metal functional layer comprises from 70 wt. % to 100 wt. % silicon and from 0 wt. % to 30 wt. % aluminum, from 80 wt. % to 95 wt. % silicon and from 5 wt. % to 20 wt. % aluminum, or from 85 wt. % to 95 wt. % silicon and from 5 wt. % to 15 wt. % aluminum.


Clause 10. The coated article of any one of clauses 1 to 3, 7, or 8, wherein the metal functional layer comprises from 30 wt. % to 85 wt. % silicon and from 15 wt. % to 70 wt. % cobalt, or from 50 wt. % to 70 wt. % silicon and from 30 wt. % to 50 wt. % cobalt.


Clause 11. The coated article of any one of clauses 1 to 10, wherein the metal functional layer is essentially free, substantially free, or completely free of iron.


Clause 12. The coated article of any one of clauses 1 to 11, further comprising a protective layer over the metal functional layer.


Clause 13. The coated article of clause 12, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or mixtures thereof.


Clause 14. The coated article of clause 12 or 13, wherein the protective layer comprises titania, silica, alumina, silicon oxide, silica aluminum oxide, silicon nitride, silicon aluminum nitride, silicon aluminum oxynitride, zirconia, or mixtures thereof.


Clause 15. The coated article of any one of clauses 12 to 14, wherein the protective layer has a thickness of from 5 nm to 70 nm, from 5 nm to 30 nm, from 30 nm to 70 nm, or from 10 nm to 30 nm.


Clause 16. The coated article of any one of clauses 1 to 15, further comprising a base layer over the glass substrate and under the metal functional layer.


Clause 17. The coated article of clause 16, wherein the metal functional layer comprises silicon.


Clause 18. The coated article of clause 16 or 17, wherein the base layer has a thickness of from 30 nm to 110 nm, from 30 nm to 80 nm, or from 70 nm to 110 nm.


Clause 19. The coated article of any one of clauses 1 to 18, further comprising at least one dielectric layer.


Clause 20. The coated article of clause 19, wherein the dielectric layer comprises one or more films selected from zinc tin oxides, zinc oxide, silica, silicon aluminum oxides, silicon nitride, aluminum nitride, silicon aluminum nitrides, titanium oxides, and titanium nitrides.


Clause 21. The coated article of clause 19 or 20, wherein each dielectric layer has a thickness of from 5 nm to 140 nm, from 80 nm to 120 nm, from 100 nm to 140 nm, or from 1 nm to 10 nm.


Clause 22. The coated article of any one of clauses 1 to 21, wherein the substrate is a glass substrate.


Clause 23. A coated article comprising: a glass substrate; and a coating over at least a portion of the substrate, the coating comprising: a dielectric layer over the substrate; a metal functional layer; and a protective layer over the metal functional layer; wherein the metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum.


Clause 24. The coated article of clause 23, wherein the metal functional layer resides over the dielectric layer; and wherein the metal functional layer comprises silicon.


Clause 25. The coated article of clause 23 or 24, further comprising a second dielectric layer over the metal functional layer; wherein the protective layer resides over the second dielectric layer.


Clause 26. The coated article of any of clauses 23 to 25, further comprising a base layer over the dielectric layer; wherein the metal functional layer resides over the base layer.


Clause 27. The coated article of clause 23, wherein the dielectric layer resides over the metal functional layer; the protective layer resides over the dielectric layer; and the metal functional layer comprises cobalt.


Clause 28. The coated article of clause 23 or 25, wherein the dielectric layer resides over the protective layer; and the metal functional layer comprises silicon.


Clause 29. The coated article of any of clauses 23 to 28, wherein the metal functional layer comprises less than 90 wt. % magnetic metals.


Clause 30. The coated article of any of clauses 23 to 29, wherein the metal functional layer has a thickness in the range of 20 nm to 40 nm, from 20 nm to 60 nm, from 30 nm to 45 nm, or from 20 nm to 30 nm.


Clause 31. The coated article of any one of clauses 23, 25 to 27, 29, or 30, wherein the metal functional layer comprises from 60 wt. % to 100 wt. % cobalt, from 60 wt. % to 90 wt. % cobalt, or from 58 wt. % to 70 wt. % cobalt.


Clause 32. The coated article of any one of clauses 23, 25 to 27, or 29 to 31, wherein the metal functional layer comprises cobalt chromium oxide.


Clause 33. The coated article of any one of clauses 23, 25 to 27, or 29 to 32, wherein the metal functional layer comprises from 60 wt. % to 100 wt. % cobalt and from 0 wt. % to 40 wt. % chromium, from 60 wt. % to 90 wt. % cobalt and from 10 wt. % to 40 wt. % chromium, or from 70 wt. % to 88 wt. % cobalt and from 12 wt. % to 30 wt. % chromium.


Clause 34. The coated article of any one of clauses 23 to 26, or 28 to 30, wherein the metal functional layer comprises from 60 wt. % to 99 wt. % silicon.


Clause 35. The coated article of any one of clauses 23 to 30, or 34, wherein the metal functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.


Clause 36. The coated article of any one of clauses 23 to 26, 28 to 30, 34, or 35, wherein the metal functional layer comprises from 70 wt. % to 100 wt. % silicon and from 0 wt. % to 30 wt. % aluminum, from 80 wt. % to 95 wt. % silicon and from 5 wt. % to 20 wt. % aluminum, or from 85 wt. % to 95 wt. % silicon and from 5 wt. % to 15 wt. % aluminum.


Clause 37. The coated article of any one of clauses 23 to 30, 34, or 35, wherein the metal functional layer comprises from 30 wt. % to 85 wt. % silicon and from 15 wt. % to 70 wt. % cobalt, or from 50 wt. % to 70 wt. % silicon and from 30 wt. % to 50 wt. % cobalt.


Clause 38. The coated article of any one of clauses 23 to 37, wherein the metal functional layer is essentially free, substantially free, or completely free of iron.


Clause 39. The coated article of any one of clauses 23 to 38, wherein the dielectric layer comprises one or more films selected from zinc tin oxides, zinc oxide, silica, silicon aluminum oxides, silicon nitride, aluminum nitride, silicon aluminum nitrides, titanium oxides, and titanium nitrides.


Clause 40. The coated article of any of clauses 23 to 39, wherein the dielectric layer comprises silicon nitride or silicon aluminum nitride.


Clause 41. The coated article of any one of clauses 23 to 40, wherein the dielectric layer has a thickness of from 5 nm to 140 nm, from 80 nm to 120 nm, from 100 nm to 140 nm, or from 1 nm to 10 nm.


Clause 42. The coated article of any one of clauses 23 to 41, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or mixtures thereof.


Clause 43. The coated article of any of clauses 23 to 42, wherein the protective layer comprises at least one of titania, silica, alumina, silicon oxide, silica aluminum oxide, silicon nitride, silicon aluminum nitride, silicon aluminum oxynitride, zirconia, or mixtures thereof.


Clause 44. The coated article of any one of clauses 23 to 43, wherein the protective layer has a thickness of from 5 nm to 70 nm, from 5 nm to 30 nm, from 30 nm to 70 nm, or from 10 nm to 30 nm.


Clause 45. The coated article of any one of clauses 26 or 29 to 44, wherein the base layer has a thickness of from 30 nm to 110 nm, from 30 nm to 80 nm, or from 70 nm to 110 nm.


Clause 46. A method of making a coated article, comprising: providing a substrate; and forming a metal functional layer over at least a portion of the substrate; wherein the metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum; and wherein the metal functional layer is formed by a process comprising depositing, by a magnetron sputtering vapor deposition method, the metal alloy, metal oxide, metal nitride, metal oxynitride, or molybdenum.


Clause 47. The method of clause 46, wherein the metal functional layer comprises less than 90 wt. % magnetic metals.


Clause 48. The method of clause 46 or 47, wherein the metal functional layer has a thickness in the range of 20 nm to 40 nm, from 20 nm to 60 nm, from 30 nm to 45 nm, or from 20 nm to 30 nm.


Clause 49. The method of any one of clauses 46 to 48, wherein the metal functional layer comprises from 60 wt. % to 100 wt. % cobalt, from 60 wt. % to 90 wt. % cobalt, or from 58 wt. % to 70 wt. % cobalt.


Clause 50. The method of any one of clauses 46 to 49, wherein the metal functional layer comprises cobalt chromium oxide.


Clause 51. The method of any one of clauses 46 to 50, wherein the metal functional layer comprises from 60 wt. % to 100 wt. % cobalt and from 0 wt. % to 40 wt. % chromium, from 60 wt. % to 90 wt. % cobalt and from 10 wt. % to 40 wt. % chromium, or from 70 wt. % to 88 wt. % cobalt and from 12 wt. % to 30 wt. % chromium.


Clause 52. The method of any one of clauses 46 to 48, wherein the metal functional layer comprises from 60 wt. % to 99 wt. % silicon.


Clause 53. The method of any one of clauses 46 to 48 or 51, wherein the metal functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.


Clause 54. The method of any one of clauses 46 to 48, 51, or 52, wherein the metal functional layer comprises from 70 wt. % to 100 wt. % silicon and from 0 wt. % to 30 wt. % aluminum, from 80 wt. % to 95 wt. % silicon and from 5 wt. % to 20 wt. % aluminum, or from 85 wt. % to 95 wt. % silicon and from 5 wt. % to 15 wt. % aluminum.


Clause 55. The method of any one of clauses 46 to 48, 51, or 52, wherein the metal functional layer comprises from 30 wt. % to 85 wt. % silicon and from 15 wt. % to 70 wt. % cobalt, or from 50 wt. % to 70 wt. % silicon and from 30 wt. % to 50 wt. % cobalt.


Clause 56. The method of any one of clauses 46 to 55, wherein the metal functional layer is essentially free, substantially free, or completely free of iron.


Clause 57. The method of any one of clauses 46 to 56, further comprising a protective layer over the metal functional layer.


Clause 58. The method of clause 57, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or mixtures thereof.


Clause 59. The method of clause 57 or 58, wherein the protective layer comprises titania, silica, alumina, silicon oxide, silica aluminum oxide, silicon nitride, silicon aluminum nitride, silicon aluminum oxynitride, zirconia, or mixtures thereof.


Clause 60. The method of any one of clauses 57 to 59, wherein the protective layer has a thickness of from 5 nm to 70 nm, from 5 nm to 30 nm, from 30 nm to 70 nm, or from 10 nm to 30 nm.


Clause 61. The method of any one of clauses 46 to 60, further comprising a base layer over the glass substrate and under the metal functional layer.


Clause 62. The method of clause 61, wherein the metal functional layer comprises silicon.


Clause 63. The method of clause 61 or 62, wherein the base layer has a thickness of from 30 nm to 110 nm, from 30 nm to 80 nm, or from 70 nm to 110 nm.


Clause 64. The coated article of any one of clauses 46 to 63, further comprising at least one dielectric layer.


Clause 65. The method of clause 64, wherein the dielectric layer comprises one or more films selected from zinc tin oxides, zinc oxide, silica, silicon aluminum oxides, silicon nitride, aluminum nitride, silicon aluminum nitrides, titanium oxides, and titanium nitrides.


Clause 66. The method of clause 64 or 65, wherein each dielectric layer has a thickness of from 5 nm to 140 nm, from 80 nm to 120 nm, from 100 nm to 140 nm, or from 1 nm to 10 nm.


Clause 67. The method of any one of clauses 46 to 66, wherein the substrate is a glass substrate.


Clause 68. A method of making a coated article, comprising: providing a substrate; and forming a coating over at least a portion of the substrate; wherein the coating comprises a dielectric layer over the substrate; a metal functional layer; and a protective layer over the metal functional layer; wherein the metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum; and wherein the metal functional layer is formed by a process comprising depositing, by a magnetron sputtering vapor deposition method, the metal alloy, metal oxide, metal nitride, metal oxynitride, or molybdenum.


Clause 69. The method of clause 68, wherein the metal functional layer resides over the dielectric layer; and wherein the metal functional layer comprises silicon.


Clause 70. The method of clause 68 or 69, further comprising a second dielectric layer over the metal functional layer; wherein the protective layer resides over the second dielectric layer.


Clause 71. The method of any of clauses 68 to 70, further comprising a base layer over the dielectric layer; wherein the metal functional layer resides over the base layer.


Clause 72. The method of clause 68, wherein the dielectric layer resides over the metal functional layer; the protective layer resides over the dielectric layer; and the metal functional layer comprises cobalt.


Clause 73. The method of clause 68 or 70, wherein the dielectric layer resides over the protective layer; and the metal functional layer comprises silicon.


Clause 74. The method of any of clauses 68 to 73, wherein the metal functional layer comprises less than 90 wt. % magnetic metals.


Clause 75. The method of any of clauses 68 to 74, wherein the metal functional layer has a thickness in the range of 20 nm to 40 nm, from 20 nm to 60 nm, from 30 nm to 45 nm, or from 20 nm to 30 nm.


Clause 76. The method of any one of clauses 68, 70 to 72, 74, or 75, wherein the metal functional layer comprises from 60 wt. % to 100 wt. % cobalt, from 60 wt. % to 90 wt. % cobalt, or from 58 wt. % to 70 wt. % cobalt.


Clause 77. The method of any one of clauses 68, 70 to 72, or 74 to 76, wherein the metal functional layer comprises cobalt chromium oxide.


Clause 78. The method of any one of clauses 68, 70 to 72, or 74 to 77, wherein the metal functional layer comprises from 60 wt. % to 100 wt. % cobalt and from 0 wt. % to 40 wt. % chromium, from 60 wt. % to 90 wt. % cobalt and from 10 wt. % to 40 wt. % chromium, or from 70 wt. % to 88 wt. % cobalt and from 12 wt. % to 30 wt. % chromium.


Clause 79. The method of any one of clauses 68 to 71, or 73 to 75, wherein the metal functional layer comprises from 60 wt. % to 99 wt. % silicon.


Clause 80. The method of any one of clauses 68 to 75, or 79, wherein the metal functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.


Clause 81. The method of any one of clauses 68 to 71, 73 to 75, 79, or 80, wherein the metal functional layer comprises from 70 wt. % to 100 wt. % silicon and from 0 wt. % to 30 wt. % aluminum, from 80 wt. % to 95 wt. % silicon and from 5 wt. % to 20 wt. % aluminum, or from 85 wt. % to 95 wt. % silicon and from 5 wt. % to 15 wt. % aluminum.


Clause 82. The method of any one of clauses 68 to 75, 79, or 80, wherein the metal functional layer comprises from 30 wt. % to 85 wt. % silicon and from 15 wt. % to 70 wt. % cobalt, or from 50 wt. % to 70 wt. % silicon and from 30 wt. % to 50 wt. % cobalt.


Clause 83. The method of any one of clauses 68 to 82, wherein the metal functional layer is essentially free, substantially free, or completely free of iron.


Clause 84. The method of any one of clauses 68 to 83, wherein the dielectric layer comprises one or more films selected from zinc tin oxides, zinc oxide, silica, silicon aluminum oxides, silicon nitride, aluminum nitride, silicon aluminum nitrides, titanium oxides, and titanium nitrides.


Clause 85. The method of any of clauses 68 to 84, wherein the dielectric layer comprises silicon nitride or silicon aluminum nitride.


Clause 86. The method of any one of clauses 68 to 85, wherein the dielectric layer has a thickness of from 5 nm to 140 nm, from 80 nm to 120 nm, from 100 nm to 140 nm, or from 1 nm to 10 nm.


Clause 87. The method of any one of clauses 68 to 86, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or mixtures thereof.


Clause 88. The method of any of clauses 68 to 87, wherein the protective layer comprises at least one of titania, silica, alumina, silicon oxide, silica aluminum oxide, silicon nitride, silicon aluminum nitride, silicon aluminum oxynitride, zirconia, or mixtures thereof.


Clause 89. The method of any one of clauses 68 to 88, wherein the protective layer has a thickness of from 5 nm to 70 nm, from 5 nm to 30 nm, from 30 nm to 70 nm, or from 10 nm to 30 nm.


Clause 90. The method of any one of clauses 71 or 74 to 89, wherein the base layer has a thickness of from 30 nm to 110 nm, from 30 nm to 80 nm, or from 70 nm to 110 nm.


Clause 91: An insulating glass unit, comprising: a first ply comprising a No. 1 surface and a No. 2 surface opposing the No. 1 surface; a second ply comprising a No. 3 surface and a No. 4 surface opposing the No. 3 surface, wherein the second ply is spaced from the first ply, and wherein the first ply and the second ply are connected together; and a coating over at least a portion of the No. 2 surface or the No. 3 surface, wherein the coating comprises: a dielectric layer over the substrate; a metal functional layer; and a protective layer over the metal functional layer; wherein the metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum.


Clause 92. The insulating glass unit of clause 91, wherein the metal functional layer resides over the dielectric layer; and wherein the metal functional layer comprises silicon.


Clause 93. The insulating glass unit of clause 91 or 92, further comprising a second dielectric layer over the metal functional layer; wherein the protective layer resides over the second dielectric layer.


Clause 94. The insulating glass unit of any of clauses 91 to 93, further comprising a base layer over the dielectric layer; wherein the metal functional layer resides over the base layer.


Clause 95. The insulating glass unit of clause 91, wherein the dielectric layer resides over the metal functional layer; the protective layer resides over the dielectric layer; and the metal functional layer comprises cobalt.


Clause 96. The insulating glass unit of clause 91 or 93, wherein the dielectric layer resides over the protective layer; and the metal functional layer comprises silicon.


Clause 97. The insulating glass unit of any of clauses 91 to 96, wherein the metal functional layer comprises less than 90 wt. % magnetic metals.


Clause 98. The insulating glass unit of any of clauses 91 to 97, wherein the metal functional layer has a thickness in the range of 20 nm to 40 nm, from 20 nm to 60 nm, from 30 nm to 45 nm, or from 20 nm to 30 nm.


Clause 99. The insulating glass unit of any one of clauses 91, 93 to 95, 97, or 98, wherein the metal functional layer comprises from 60 wt. % to 100 wt. % cobalt, from 60 wt. % to 90 wt. % cobalt, or from 58 wt. % to 70 wt. % cobalt.


Clause 100. The insulating glass unit of any one of clauses 91, 93 to 95, or 97 to 99, wherein the metal functional layer comprises cobalt chromium oxide.


Clause 101. The insulating glass unit of any one of clauses 91, 93 to 95, or 97 to 100, wherein the metal functional layer comprises from 60 wt. % to 100 wt. % cobalt and from 0 wt. % to 40 wt. % chromium, from 60 wt. % to 90 wt. % cobalt and from 10 wt. % to 40 wt. % chromium, or from 70 wt. % to 88 wt. % cobalt and from 12 wt. % to 30 wt. % chromium.


Clause 102. The insulating glass unit of any one of clauses 91 to 94, or 96 to 98, wherein the metal functional layer comprises from 60 wt. % to 99 wt. % silicon.


Clause 103. The insulating glass unit of any one of clauses 91 to 98, or 102, wherein the metal functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.


Clause 104. The insulating glass unit of any one of clauses 91 to 94, 96 to 98, 102, or 103, wherein the metal functional layer comprises from 70 wt. % to 100 wt. % silicon and from 0 wt. % to 30 wt. % aluminum, from 80 wt. % to 95 wt. % silicon and from 5 wt. % to 20 wt. % aluminum, or from 85 wt. % to 95 wt. % silicon and from 5 wt. % to 15 wt. % aluminum.


Clause 105. The insulating glass unit of any one of clauses 91 to 98, 111, or 112, wherein the metal functional layer comprises from 30 wt. % to 85 wt. % silicon and from 15 wt. % to 70 wt. % cobalt, or from 50 wt. % to 70 wt. % silicon and from 30 wt. % to 50 wt. % cobalt.


Clause 106. The insulating glass unit of any one of clauses 91 to 105, wherein the metal functional layer is essentially free, substantially free, or completely free of iron.


Clause 107. The insulating glass unit of any one of clauses 91 to 106, wherein the dielectric layer comprises one or more films selected from zinc tin oxides, zinc oxide, silica, silicon aluminum oxides, silicon nitride, aluminum nitride, silicon aluminum nitrides, titanium oxides, and titanium nitrides.


Clause 108. The insulating glass unit of any of clauses 91 to 107, wherein the dielectric layer comprises silicon nitride or silicon aluminum nitride.


Clause 109. The method of any one of clauses 91 to 108, wherein the dielectric layer has a thickness of from 5 nm to 140 nm, from 80 nm to 120 nm, from 100 nm to 140 nm, or from 1 nm to 10 nm.


Clause 110. The insulating glass unit of any one of clauses 91 to 109, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or mixtures thereof.


Clause 111. The insulating glass unit of any of clauses 91 to 110, wherein the protective layer comprises at least one of titania, silica, alumina, silicon oxide, silica aluminum oxide, silicon nitride, silicon aluminum nitride, silicon aluminum oxynitride, zirconia, or mixtures thereof.


Clause 112. The insulating glass unit of any one of clauses 91 to 111, wherein the protective layer has a thickness of from 5 nm to 70 nm, from 5 nm to 30 nm, from 30 nm to 70 nm, or from 10 nm to 30 nm.


Clause 113. The insulating glass unit of any one of clauses 94 or 97 to 112, wherein the base layer has a thickness of from 30 nm to 110 nm, from 30 nm to 80 nm, or from 70 nm to 110 nm.


The following Examples illustrate various embodiments of the invention. However, it is to be understood that the invention is not limited to these specific embodiments.


Examples

Table 1 shows exemplary coated articles 1-4 of the invention. The reported thicknesses are physical thicknesses in nanometers (nm). The substrate was 6 mm clear glass. A cobalt chromium oxide (CoCrOx) layer was deposited on the glass substrate by MSVD using a Co80Cr20 (80 wt. % cobalt and 20 wt. % chromium) or a Co80Cr15 (85 wt. % cobalt and 15 wt. % chromium) target. A silicon nitride (SiNx) layer was optionally deposited over the cobalt chromium oxide layer. An outer protective layer of silicon aluminum oxide (SiAlOx) was deposited.













TABLE 1





Sample
1
2
3
4























SiAlOx
20
nm
20
nm
10
nm
20
nm


SINx
0
nm
0
nm
5
nm
5
nm


CoCrOx
35
nm
30
nm
37
nm
37
nm











Substrate
6 mm glass
6 mm glass
6 mm glass
6 mm glass









Table 2 shows exemplary coated articles 5-7 of the invention. The reported thicknesses are physical thicknesses in nm. The substrate was 6 mm clear glass. A silicon aluminum metal alloy (SiAl) layer was deposited on the glass substrate by MSVD using a Si95Al5 alloy (95 wt. % silicon and 5 wt. % aluminum) target. An outer protective layer of silicon aluminum oxide (SiAlOx) was deposited over the SiAl layer.












TABLE 2





Sample
5
6
7







SiAlOx
35 nm
35 nm
50 nm


SiAl metal alloy
30 nm
40 nm
30 nm


Substrate
6 mm glass
6 mm glass
6 mm glass









Table 3 shows exemplary coated articles 8-13 of the invention. The reported thicknesses are physical thicknesses in nm. The substrate was 6 mm clear glass. A silicon cobalt metal alloy (SiCo) layer was deposited on the glass substrate by MSVD using a Si70Co30 alloy (70 wt. % silicon and 30 wt. % cobalt) target. An outer protective layer of silicon aluminum oxide (SiAlOx) was deposited over the SiCo layer.















TABLE 3





Sample
8
9
10
11
12
13







SiAlOx
60 nm
60 nm
60 nm
40 nm
40 nm
40 nm


SiCo metal
10 nm
15 nm
20 nm
10 nm
15 nm
20 nm


alloy


Substrate
6 mm
6 mm
6 mm
6 mm
6 mm
6 mm



glass
glass
glass
glass
glass
glass









Table 4 shows exemplary coated articles 14-16 of the invention. The reported thicknesses are physical thicknesses in nm. The substrate was 6 mm clear glass. A silicon aluminum nitride (SiAlNx) layer was optionally deposited on the glass substrate (Sample 14). A silicon cobalt metal alloy (SiCo) layer was deposited on the glass substrate (Samples 15 and 16) or over the optional SiAlNx layer (Sample 14) by MSVD using a Si70Co30 alloy (70 wt. % silicon and 30 wt. % cobalt) target. A silicon aluminum oxide (SiAlOx) layer was optionally deposited over the SiCo layer (Samples 14 and 15). A SiAlNx layer was optionally deposited over the optional SiAlOx layer (Sample 15) or the SiCo layer (Sample 16). Another SiAlOx layer was optionally deposited over the optional SiAlNx layer (Sample 16).
















TABLE 4







Sample

14

15
16
























SiAlOx
0
nm
0
nm
50
nm



SiAlNx
0
nm
10
nm
10
nm



SiAlOx
50
nm
50
nm
0
nm



SiCo metal
15
nm
15
nm
15
nm



SiAlNx
10
nm
0
nm
0
nm












Substrate
6 mm glass
6 mm glass
6 mm glass










Table 5 shows exemplary coated articles 17-24 of the invention. The reported thicknesses are physical thicknesses in nm. The substrate was 6 mm clear glass. A first silicon aluminum nitride (SiAlNx) layer was deposited on the glass surface. A silicon cobalt metal alloy (SiCo) layer was deposited on the SiAlNx layer by MSVD using a Si70Co30 alloy (70 wt. % silicon and 30 wt. % cobalt) target. A second SiAlNx layer was deposited over the SiCo layer. An optional protective layer of silicon aluminum oxide (SiAlOx) was deposited over the second SiAlNx layer.

















TABLE 5





Sample
17
18
19
20
21
22
23
24







SiAlOx
 0 nm
 0 nm
 0 nm
 0 nm
10 nm
10 nm
10 nm
10 nm


SiAlNx
22 nm
16 nm
20 nm
12 nm
20 nm
18 nm
16 nm
14 nm


SiCo metal
12 nm
12 nm
12 nm
12 nm
12 nm
12 nm
12 nm
12 nm


alloy


SiAlNx
18 nm
20 nm
20 nm
20 nm
18 nm
18 nm
18 nm
18 nm


Substrate
6 mm
6 mm
6 mm
6 mm
6 mm
6 mm
6 mm
6 mm



glass
glass
glass
glass
glass
glass
glass
glass









Spectral Properties

Table 6 shows spectral properties for Samples 1-4 of Table 1. “T” refers to transmittance, “Rf” refers to film side or coating side reflection, and “Rg” refers to glass side reflection.



















TABLE 6





Sample
T L*
T a*
T b*
LTA
Rf L*
Rf a*
Rf b*
Rg L*
Rg a*
Rg b*

























1
70.17
2.64
10.09
42.61
62.89
−4.34
3.72
57.65
−5.28
3.40


2
72.59
2.83
9.96
46.27
61.28
−4.57
1.27
55.52
−5.45
1.41


3
70.04
2.84
9.71
42.42
63.08
−4.32
4.32
58.50
−5.14
3.10


4
70.92
2.56
8.91
43.57
61.91
−4.29
6.70
59.05
−4.95
3.31









Table 7 shows spectral properties for Samples 8-13 of Table 3.



















TABLE 7





Sample
T L*
T a*
T b*
LTA
Rf L*
Rf a*
Rf b*
Rg L*
Rg a*
Rg b*

























8
74.11
0.97
7.46
48.02
39.37
−3.33
7.33
48.47
−5.56
−9.02


9
65.92
1.77
8.94
36.44
47.60
−3.85
3.98
55.16
−6.48
−8.81


10
59.44
1.87
9.89
28.62
53.32
−3.74
3.18
59.99
−6.60
−7.15


11
72.64
1.39
7.77
45.85
47.99
−4.09
−0.51
43.76
−5.53
−9.77


12
63.79
2.46
9.89
33.89
55.70
−4.78
−1.34
52.41
−6.80
−10.05


13
57.13
2.66
10.72
26.27
60.95
−4.65
−1.03
57.92
−7.10
−8.78









Table 8 shows spectral properties for Samples 14-16 of Table 4.



















TABLE 8





Sample
T L*
T a*
T b*
LTA
Rf L*
Rf a*
Rf b*
Rg L*
Rg a*
Rg b*

























14
65.39
1.54
8.44
35.65
49.48
−4.15
3.77
54.39
−6.65
−9.22


15
63.86
1.61
8.26
33.68
55.09
−4.09
1.88
55.27
−6.70
−7.92


16
64.74
1.72
8.18
34.82
50.92
−4.50
4.79
56.13
−6.77
−8.96









Table 9 shows spectral properties for Samples 21-24 of Table 5.



















TABLE 9





Sample
T L*
T a*
T b*
LTA
Rf L*
Rf a*
Rf b*
Rg L*
Rg a*
Rg b*

























21
63.86
2.29
7.19
33.70
61.53
−4.56
1.08
56.68
−6.68
−5.61


22
63.85
2.37
7.79
33.76
62.17
−4.54
−0.39
55.73
−6.83
−5.66


23
63.37
2.43
8.08
33.19
62.50
−4.55
−0.68
55.68
−6.85
−5.78


24
62.87
2.55
8.63
32.65
63.62
−4.38
−2.63
53.86
−6.88
−5.36









DURABILITY PROPERTIES

The CCC test results for Samples 1 to 4 after heating (60° C. DI water chamber) are shown in FIGS. 9A-9D. For the coatings with no silicon aluminum nitride (SiAlNx) layer (Samples 1 and 2), the color changes (DECMC T, Rf) were larger than 2 after 20 days. However, the coatings with a thin SiNx layer (Samples 3 and 4) in between the CoCrOx and the protective layer showed color changes (DECMC T, Rf) of less than 1 after 50 days and pass the CCC test.


Samples 1-4 passed the Standard Chemical Durability Test. Samples 1-4 showed less than 12% film loss after 30 minutes immersion in 10N (27.5%) sulfuric acid at 52° C.


The passing CCC test results for Sample 7 (after heating, 60° C. DI water chamber) are shown in FIGS. 10A and 10B. The film side reflectance color change (DECMC of Rf, FIG. 10A) and the transmittance color change (DECMC of T, FIG. 10B) were less than 0.5 after 50 days. Sample 7 passed the Standard Chemical Durability Test.


Table 10 shows the CCC test results for Samples 8 to 13 (after heating, 60° C. DI water chamber). The abbreviation “n.d.” refers to “not determined”.














TABLE 10







Sample
T, DECMC
Rf, DECMC
Rg, DECMC





















8
4.26
18.71
14.01



9
n.d.
11.09
12.79



10
5.12
7.03
11.73



11
3.33
10.64
15.87



12
n.d.
6.28
13.65



13
6.39
n.d.
12.65










Table 11 shows the CCC test results for Samples 14 to 16.














TABLE 11







Sample
T, DECMC
Rf, DECMC
Rg, DECMC





















14
2.32
9.73
13.04



15
2.73
5.66
12.06



16
2.27
9.15
12.80










The CCC test results Samples 17 to 24 (after heating, 60° C. DI water chamber) are shown in FIGS. 11A-11D. The coatings with no protective layer (Samples 17 to 20, FIGS. 11C and 11D) did not pass the CCC test. However, the coatings with a protective layer (Samples 21 to 24, FIGS. 11A and 11B) showed a film side reflectance color change (DECMC of Rf, FIG. 11A) of less than 1 and a transmittance color change (DECMC of T, FIG. 11B) of less than 0.5 after 50 days.


It will be readily appreciated by those skilled in the art that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. Accordingly, the particular embodiments described in detail herein are illustrative only and are not limiting to the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalents thereof.

Claims
  • 1. A coated article comprising: a substrate; anda metal functional layer over at least a portion of the substrate;wherein the metal functional layer comprises: a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, and cobalt aluminum iron oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, and cobalt aluminum iron nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, and cobalt aluminum iron oxynitride, or molybdenum.
  • 2. The coated article of claim 1, wherein the metal functional layer comprises less than 90 wt. % magnetic metals.
  • 3. The coated article of claim 1, wherein the metal functional layer has a thickness in the range of 20 nm to 40 nm.
  • 4. The coated article of claim 1, wherein the metal functional layer comprises from 60 wt. % to 100 wt. % cobalt.
  • 5. The coated article of claim 4, wherein the metal functional layer comprises cobalt chromium oxide.
  • 6. The coated article of claim 1, wherein the metal functional layer comprises from 60 wt. % to 99 wt. % silicon.
  • 7. The coated article of claim 6, wherein the metal functional layer comprises a silicon aluminum alloy or a silicon cobalt alloy.
  • 8. The coated article of claim 1, further comprising a protective layer over the metal functional layer, wherein the protective layer comprises a metal oxide layer, a metal nitride layer, or mixtures thereof.
  • 9. The coated article of claim 8, wherein the protective layer comprises titania, silica, alumina, silicon oxide, silica aluminum oxide, silicon nitride, silicon aluminum nitride, silicon aluminum oxynitride, zirconia, or mixtures thereof.
  • 10. The coated article of claim 8, further comprising a base layer over the substrate and under the metal functional layer; wherein the metal functional layer comprises silicon.
  • 11. The coated article of claim 1, further comprising at least one dielectric layer.
  • 12. The coated article of claim 11, wherein the dielectric layer comprises one or more films selected from zinc tin oxides, zinc oxide, silica, silicon aluminum oxides, silicon nitride, aluminum nitride, silicon aluminum nitrides, titanium oxides, and titanium nitrides.
  • 13. A coated article comprising: a glass substrate; anda coating over at least a portion of the substrate, the coating comprising: a dielectric layer over the substrate;a metal functional layer; anda protective layer over the metal functional layer;wherein the metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum.
  • 14. The coated article of claim 13, wherein the metal functional layer resides over the dielectric layer; and wherein the metal functional layer comprises silicon.
  • 15. The coated article of claim 14, further comprising a second dielectric layer over the metal functional layer; wherein the protective layer resides over the second dielectric layer.
  • 16. The coated article of claim 14, further comprising a base layer over the dielectric layer; wherein the metal functional layer resides over the base layer.
  • 17. The coated article of claim 13, wherein the dielectric layer resides over the metal functional layer; the protective layer resides over the dielectric layer; andthe metal functional layer comprises cobalt.
  • 18. The coated article of claim 13, wherein the dielectric layer resides over the protective layer; and the metal functional layer comprises silicon.
  • 19. The coated article of claim 15, wherein the dielectric layer comprises silicon nitride or silicon aluminum nitride.
  • 20. A method of making a coated article, comprising: providing a substrate; andforming a metal functional layer over at least a portion of the substrate;wherein the metal functional layer comprises a metal alloy selected from the group consisting of a silicon aluminum alloy, a silicon cobalt alloy, a niobium tungsten alloy, and a titanium tungsten alloy, or a metal oxide selected from the group consisting of cobalt oxide, cobalt iron oxide, cobalt chromium oxide, cobalt iron chromium oxide, cobalt copper oxide, cobalt aluminum chromium oxide, cobalt aluminum iron oxide, and zinc iron chromium oxide, or a metal nitride selected from the group consisting of cobalt nitride, cobalt iron nitride, cobalt chromium nitride, cobalt iron chromium nitride, cobalt copper nitride, cobalt aluminum chromium nitride, cobalt aluminum iron nitride, and zinc iron chromium nitride, or a metal oxynitride selected from the group consisting of cobalt oxynitride, cobalt iron oxynitride, cobalt chromium oxynitride, cobalt iron chromium oxynitride, cobalt copper oxynitride, cobalt aluminum chromium oxynitride, cobalt aluminum iron oxynitride, and zinc iron chromium oxynitride, or molybdenum; andwherein the metal functional layer is formed by a process comprising depositing, by a magnetron sputtering vapor deposition method, the metal alloy, metal oxide, metal nitride, metal oxynitride, or molybdenum.
CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Application No. 63/406,291, filed Sep. 14, 2022, the disclosure of which is incorporated by reference in its entirety.

Provisional Applications (1)
Number Date Country
63406291 Sep 2022 US